EP0491393B1 - Vertically oriented CVD apparatus including gas inlet tube having gas injection holes - Google Patents

Vertically oriented CVD apparatus including gas inlet tube having gas injection holes Download PDF

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Publication number
EP0491393B1
EP0491393B1 EP91121791A EP91121791A EP0491393B1 EP 0491393 B1 EP0491393 B1 EP 0491393B1 EP 91121791 A EP91121791 A EP 91121791A EP 91121791 A EP91121791 A EP 91121791A EP 0491393 B1 EP0491393 B1 EP 0491393B1
Authority
EP
European Patent Office
Prior art keywords
cvd apparatus
gas inlet
inlet tube
vertically oriented
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91121791A
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German (de)
English (en)
French (fr)
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EP0491393A3 (en
EP0491393A2 (en
Inventor
Shinji c/o Intellectual Property Div. Miyazaki
Yuichi c/o Intellectual Property Div. Mikata
Takahiko c/o Intellectual Property Div. Moriya
Reiji Niino
Motohiko Nishimura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Tokyo Electron Ltd
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Toshiba Corp
Tokyo Electron Ltd
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Application filed by Toshiba Corp, Tokyo Electron Ltd filed Critical Toshiba Corp
Publication of EP0491393A2 publication Critical patent/EP0491393A2/en
Publication of EP0491393A3 publication Critical patent/EP0491393A3/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45578—Elongated nozzles, tubes with holes
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C30B25/14—Feed and outlet means for the gases; Modifying the flow of the reactive gases

Definitions

  • the present invention relates to a vertical-type CVD apparatus for forming films, such as silicon nitride films, on semiconductor substrates.
  • Fig. 9 schematically shows in cross section an example of a vertical-type CVD apparatus, which is a type of conventional CVD apparatus corresponding to that shown in JP-A-2-174 224.
  • Numeral 11 denotes an inner tube which is made of quartz, 12 an outer tube which is also made of quartz, 13 a manifold flange, 14 a cover, and 15 an O-ring.
  • These components constitute a reduced pressure CVD chamber 10.
  • a pedestal 17, which is coupled to a rotational mechanism 16 provided outside the CVD chamber 10, is arranged in the inner tube 11, and a quartz boat 18 is mounted on the pedestal 17.
  • a heater 19 for keeping the CVD chamber 10 at a desired temperature is provided outside the chamber 10 (the temperature distribution within the chamber is as shown in Fig. 10, for example).
  • a plurality of semiconductor substrates 20 are horizontally arranged parallel to each other and spaced a predetermined distance apart from one another.
  • the manifold flange 13 has an exhaust port 21 to which an external exhaust means is coupled to maintain the chamber at a reduced pressure.
  • the manifold flange 13 also has a plurality of raw gas inlet ports, for example, to raw gas inlet ports 221 and 222, through which gas inlet tubes 231 and 232 are inserted into the CVD chamber. At least one of the two gas inlet tubes (e.g., the tube 231) has a portion extending beside the substrates into the uppermost inner region of the reaction chamber.
  • the gas inlet tube 231 has a closed distal end, and is also provided with gas injection holes 34 along its longitudinal direction.
  • the other gas inlet tube 232 has a portion extending up to the pedestal 17 arranged in the inner tube 11.
  • Reference numeral 24 denotes a transfer mechanism.
  • raw gases e.g., dichlorosilane gas and ammonia gas
  • a CVD film e.g., silicon nitride film
  • the reason for locating the substrates 20 in the uniformly-heated zone is to prevent silicon nitride films, each being deposited on the substrates 20, from having a variation in the film thickness, based on their position in the boat 18.
  • a single gas inlet tube 30, shown in Figs. 11A and 11B can be used.
  • the distal end of the tube 30 is closed, and the proximal end portion thereof is divided into two branches.
  • An injector nozzle portion 33 which is at a higher positional level than a branch portion 31 of the gas inlet tube 30, has a plurality of gas injection holes 34, and raw gases are supplied independently through two gas inlet ports 321 and 322, which are provided at the distal end of each of the branches. It has been proposed that by using such a gas inlet tube, the raw gases with a uniform concentration can be supplied to the aforementioned uniformly-heated zone (Published Unexamined Japanese Utility Model Application 64-37464, for example).
  • the variation in the film thickness among the substrates can be controlled by use of the batch processing mentioned above.
  • a variation in essential properties (film quality and composition) of the deposited silicon nitride films is not negligible.
  • the hydrofluoric acid (HF) etching rate and the refractive index of the silicon nitride film relative to the position of the substrate 20 were measured.
  • the result of the measurements is shown in Figs. 12 and 13.
  • the composition of each silicon nitride film differs considerably from one another according to substrate positions.
  • the CVD films formed on substrates should ideally have the uniform thickness and composition.
  • forming CVD films with the uniform thickness is the main consideration; the variation in film composition among the substrates is disregarded.
  • the composition of the CVD films is intended to make it uniform among the substrates by using the conventional CVD apparatus, the desired results can not be obtained even if the atmospheric condition and the flow rate of raw gases are changed. Therefore, it is necessary to keep the uniformly heated zone at a constant temperature without the temperature gradient. However, such a technique is not used because the throughput of the batch processing, which is a merit of the CVD apparatus, is remarkably reduced.
  • the problem described above may be somewhat improved if the gas inlet tube 30, whose proximal end portion is divided into two branches as shown in Figs. 11A and 11B, is employed.
  • the gas inlet tube 30 if the gas inlet tube 30 is used, the thickness of the deposited CVD film is different between the central portion of the substrate and the peripheral portion. That is, the difference of the film thickness is considerably large within the plane of the substrate. This is because each of the gas injection holes faces toward the central axis of its corresponding substrate.
  • a conventional vertical-type CVD apparatus has the merits that CVD films can be formed on a plurality of substrates in a single batch and the films thus formed are of uniform in thickness, whereas it has the drawback that the characteristics of the formed CVD films differ.
  • EP-A-0 164 928 shows a vertical hot-wall reactor for CVD with gas inlet means with a plurality of manifolds each having a plurality of orifices.
  • a vertically oriented CVD apparatus which comprises a reaction chamber, a boat means vertically placed in the reaction chamber to horizontally support a plurality of semiconductor substrates, and a gas inlet tube including a plurality of gas injection holes along a longitudinal axis thereof and also extending along a longitudinal side of the boat means to introduce a reaction gas into the reaction chamber.
  • a direction of each of the gas injection holes is set at an angle ⁇ with respect to a reference line given by a straight line connecting a center of the gas inlet tube to a center of one of the substrates, and further the angle ⁇ is defined by 0° ⁇ ⁇ ⁇ 90°.
  • the conventional vertical-type CVD apparatus shown in Fig. 9 employs two gas inlet tubes 231 and 232
  • the vertical-type CVD apparatus shown in Fig. 1 employs, in place of the tubes 231 and 232, a gas inlet tube 30' whose proximal end portion is divided into two branches as shown in Figs. 11A and 11B and whose distal end is closed.
  • the gas inlet tube 30' has a plurality of gas injection holes 34. A direction of each gas injection hole 34 is set as explained hereinafter.
  • the parts of the apparatus shown in Fig. 1 and corresponding to those of the conventional apparatus shown in Fig. 9 are denoted by the same reference numerals.
  • raw gases are supplied independently through gas inlet ports 221 and 222 of the gas inlet tube 30'.
  • the gases are mixed with each other while flowing within the inlet tube (normally, raw gases are mixed in the vicinity of a branch portion 31 where no dust and by-products are produced), and the mixed gas is introduced into a reaction chamber through the gas injection holes 34.
  • Fig. 2 schematically shows a plan view of the middle portion of the reduced pressure CVD apparatus 10.
  • 11 is the inner tube, and 18 is the boat for holding a plurality of substrates.
  • 20 is one of 15.2cm (6-inch) silicon substrates (wafers) which are horizontally held by the boat 18, and 20a is the orientation flat of the substrate 20.
  • 30' is a gas inlet tube, and 34 is a plurality of gas injection holes of the gas inlet tube 30'.
  • A is a straight line connecting a center P of the gas inlet tube to a center 0 of the substrate, which is given as a reference line.
  • B is a straight line connecting the center P of the gas inlet tube and a given point on the periphery of the substrate 20 (i.e.
  • ⁇ is a direction of one gas injection hole 34 with respect to the reference line A, which is given by angle between the reference line A and a straight line C passing through the center P of the gas inlet tube.
  • ⁇ 0 is an angle given by the tangent B, passing through the center P of the gas inlet tube;-with respect to the reference line A.
  • l is a distance between an edge of the gas inlet tube 30' and an edge of the substrate 20.
  • the direction ⁇ of the gas injection hole 34 of the gas inlet tube 30' is set in a predetermined range which is larger than ⁇ 0.
  • Each of the gas injection holes 34 is arranged in the same direction or different directions within the predetermined range.
  • Figs. 3 to 6 show experimental results on a distribution of a thickness of deposited films where the direction ⁇ of the gas injection hole 34, the distance l between the gas inlet tube 30' and the substrate 20 and the diameter d of the gas injection hole 34 were changed as parameters when a plurality of substrates 20 were placed in the uniformly-heated zone of the vertical-type CVD apparatus illustrated in Fig. 1, and raw gases (e.g. dichlorosilane gas and ammonium gas) were supplied to form silicon nitride films on the substrates 20.
  • raw gases e.g. dichlorosilane gas and ammonium gas
  • Fig. 3 shows an example of the results where ⁇ is changed in the range of 0° ⁇ ⁇ ⁇ 90°, (the angle ⁇ 0 is changed in the range of 0 to ⁇ 45°).
  • the distance l between the gas inlet tube and the substrate, and the diameter d of each gas injection hole are set to optimum values (the distance l and the diameter d are given by 15 mm and 1.0 mm, respectively).
  • Fig. 4 shows a distribution of the film thickness relative to the positions of substrates 20 (i.e. the distance from the inlet port of the reaction chamber) when the silicon nitride film was deposited on the substrates by means of both the CVD apparatus of this embodiment and the conventional CVD apparatus, respectively, while keeping the uniformly-heated zone at a substantially constant temperature.
  • the direction ⁇ of the gas injection hole, the distance l between the gas inlet tube and the substrate, and the diameter d of the gas injection hole are optimized (e.g., ⁇ is given by 45° that is the same direction as the tangent B, l is 15 mm and d is 1.0 mm, respectively).
  • Fig. 5 shows an example of the results where the distance l between the edge of the gas inlet tube 30' and the edge of the substrate 20 is varied in the range of 10 to 20 mm (it is impossible to reduce the distance l to below 10 mm because unwanted interference occurs between the substrate and the gas injection holes).
  • the direction ⁇ of the gas injection hole and the distance l between the gas inlet tube and the substrate are optimized (e.g. ⁇ is given by 45° that is the same direction as the tangent B, and l is 15 mm respectively.).
  • Fig. 6 shows an example of the results where the diameter d of the gas injection hole is varied in the range of 0.5 to 1.5 mm.
  • the direction ⁇ of the gas injection hole and the distance l between the gas inlet tube and the substrate are optimized (e.g. ⁇ is given by 45° that is the same direction as the tangent B, and l is 15 mm).
  • Figs. 7 and 8 show examples of the results where the variation in characteristics of the silicon nitride film among the substrates is investigated when the silicon nitride film was deposited on each substrate 20 under optimized conditions of ⁇ , l, and d .
  • Fig. 7 shows an example of the results where the distribution of the HF etching rate of the silicon nitrdie films relative to the positions of the substrates (the distance from the inlet port of the reaction chamber) was measured
  • Fig. 8 shows an example of the results where the distribution of the refractive index of the silicon nitride film relative to the positions of the substrates on the boat (the distances from the inlet port of the reaction chamber) was measured.
  • CVD films such as silicon nitride films.
  • an impurity gas PH3 gas, B2H6 gas, etc
  • CVD films which are substantially uniform in thickness and composition can be formed on a plurality of substrates.
  • the CVD films thus formed can be treated to have substantially the same state in the case where they are etched. Further, according to the present invention, the differences in the characteristics of the films on the wafers are small even in the case of using a CVD film itself as a part of the semiconductor.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
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EP91121791A 1990-12-19 1991-12-19 Vertically oriented CVD apparatus including gas inlet tube having gas injection holes Expired - Lifetime EP0491393B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP403943/90 1990-12-19
JP2403943A JP2839720B2 (ja) 1990-12-19 1990-12-19 熱処理装置

Publications (3)

Publication Number Publication Date
EP0491393A2 EP0491393A2 (en) 1992-06-24
EP0491393A3 EP0491393A3 (en) 1993-03-03
EP0491393B1 true EP0491393B1 (en) 1996-03-27

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EP91121791A Expired - Lifetime EP0491393B1 (en) 1990-12-19 1991-12-19 Vertically oriented CVD apparatus including gas inlet tube having gas injection holes

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US (1) US5252133A (ko)
EP (1) EP0491393B1 (ko)
JP (1) JP2839720B2 (ko)
KR (1) KR950001839B1 (ko)
DE (1) DE69118337T2 (ko)

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EP0491393A3 (en) 1993-03-03
EP0491393A2 (en) 1992-06-24
DE69118337T2 (de) 1996-09-05
DE69118337D1 (de) 1996-05-02
JP2839720B2 (ja) 1998-12-16
US5252133A (en) 1993-10-12
KR920013632A (ko) 1992-07-29
KR950001839B1 (ko) 1995-03-03
JPH04218916A (ja) 1992-08-10

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